Stable, high-yield reforming catalyst

ABSTRACT

A reforming process, selective for the dehydrocyclization of paraffins to aromatics, is effected using a catalyst containing multiple Group VIII (8-10) noble metals having different gradients within the catalyst and a nonacidic large-pore molecular sieve. The use of this bed of catalyst results in greater selectivity of conversion of paraffins to aromatics and improved catalyst stability, particularly in the presence of small amounts of sulfur.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of prior application Ser. No. 08/445,620,filed May 22, 1995, U.S. Pat. No. 5,614,454 which is acontinuation-in-part of Ser. No. 08/378,117, filed Jan. 24, 1995, U.S.Pat. No. 5,464,800; which is a continuation-in-part of application Ser.No. 08/194,973, filed Feb. 14, 1994, U.S. Pat. No. 5,384,038, which is adivision of Ser. No. 07/974,544, filed Nov. 12, 1992, U.S. Pat. No.5,314,854, the contents of all of which are incorporated herein byreference thereto.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a catalyst and process for the conversion ofhydrocarbons, and more specifically for the catalytic reforming ofgasoline-range hydrocarbons.

2. General Background

The catalytic reforming of hydrocarbon feedstocks in the gasoline rangeis an important commercial process, practiced in nearly everysignificant petroleum refinery in the world to produce aromaticintermediates for the petrochemical industry or gasoline components withhigh resistance to engine knock. Demand for aromatics is growing morerapidly than the supply of feedstocks for aromatics production.Moreover, the widespread removal of lead antiknock additive fromgasoline, reformulation of gasoline for reduced emissions, and therising demands of high-performance internal-combustion engines areincreasing the required knock resistance of the gasoline component asmeasured by gasoline "octane" number. The catalytic reforming unittherefore must operate more efficiently at higher severity in order tomeet these increasing aromatics and gasoline-octane needs. This trendcreates a need for more effective reforming processes and catalysts.

Catalytic reforming generally is applied to a feedstock rich inparaffinic and naphthenic hydrocarbons and is effected through diversereactions: dehydrogenation of naphthenes to aromatics,dehydrocyclization of paraffins, isomerization of paraffins andnaphthenes, dealkylation of alkylaromatics, hydrocracking of paraffinsto light hydrocarbons, and formation of coke which is deposited on thecatalyst. Increased aromatics and gasoline-octane needs have turnedattention to the paraffin-dehydrocyclization reaction, which is lessfavored thermodynamically and kinetically in conventional reforming thanother aromatization reactions. Considerable leverage exists forincreasing desired product yields from catalytic reforming by promotingthe dehydrocyclization reaction over the competing hydrocrackingreaction while minimizing the formation of coke.

The effectiveness of reforming catalysts comprising a non-acidicL-zeolite and a platinum-group metal for dehydrocyclization of paraffinsis well known in the art. The use of these reforming catalysts toproduce aromatics from paraffinic raffinates as well as naphthas hasbeen disclosed. The increased sensitivity of these selective catalyststo sulfur in the fed also is known. Commercialization has been slow incoming and is limited in scope, however, in light of the specialmeasures that must be taken to exclude sulfur from the process. There isa need for a more sulfur-tolerant reforming process which will utilizethe high selectivity featured by these dehydrocyclization catalysts.

3. Related Art

The art discloses reforming with a broad range of catalysts containinglarge-pore zeolites and Group VIII metals. U.S. Pat. No. 4,104,320(Bernard et al.) discloses dehydrocyclization with potassium-formL-zeolite charged with one or more dehydrogenating metals of Group VIII,but teaches that two metals would be introduced simultaneously and doesnot suggest the advantages of controlling the distribution of metal inthe catalyst. U.S. Pat. No. 4,914,068 (Cross et al.) teaches a method ofdispersing at least one Group VIII metal in the pores of a large porezeolite, along with a specified amount of a non-platinum metal salt.

Non-uniform distribution of metal within a catalyst is known in the art.U.S. Pat. No. 3,259,589 (Michalko) discloses a variety of catalystphysical structure characterized by the placement of a layer of a metalcomponent, but does not suggest that the metal component should comprisemetals with different gradients. A surface-impregnated Group VIII noblemetal component of a catalyst is taught in U.S. Pat. Nos. 3,651,167 (deRosset et al.) and 3,897,368 (Ohara et al.), which do not suggestdifferent gradients of different metals. U.S. Pat. No. 4,544,645(Klassen et al.) discloses a particulate solid cracking catalyst whichcontains platinum and palladium to minimize nitrogen oxides whilepromoting the oxidation of sulfur oxides. U.S. Pat. No. 4,677,094 (Moseret al.) teaches a trimetallic catalyst comprising uniform platinum andtin and a surface-impregnated metal selected from one or more ofrhodium, ruthenium, cobalt, nickel, and iridium, and teaches that thesurface-impregnated component is incorporated into the catalyst supportof an acidic catalyst. U.S. Pat. No. 4,786,625 (Imai et al.) teaches acatalytic composite comprising surface-impregnated platinum group metaland uniform tin, germanium, or rhenium on a refractory oxide support.U.S. Pat. No. 4,992,158 (Schweizer) teaches the introduction of platinumor palladium near the surface of preferably L-zeolite using Pt and/or Pdacetylacetonate; different gradients of different metals are notsuggested, however. U.W. Patent 5,017,541 (Schmidt et al.) teaches acatalyst particle having a surface-layer platinum-group metal componentfor low-temperature isomerization. None of the above referencesanticipate or suggest a catalyst containing a nonacidic large-poremolecular sieve and two or more platinum-group metals having differentgradients within the catalyst.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a catalyst systemfor a catalytic system for a catalytic reforming process effective forthe dehydrocyclization of paraffins with high catalyst activity andstability. A corollary objective is to avoid sulfur deactivation of areforming catalyst in which high selectivity of paraffindehydrocyclization generally is associated with unusual feed-sulfurintolerance.

This invention is based on the discovery that a bound L-zeolite catalystcontaining a surface-layer palladium component and uniformly dispersedplatinum results in substantial improvements in catalyst activity andstability as well as selectivity to aromatics in a catalytic reformingprocess.

A broad embodiment of the present invention is a catalyst particlecontained within a bed of catalyst particles, selective fordehydrocyclization of paraffins, comprising a bound nonacidic large-poremolecular sieve and a multimetallic, multigradient Group VIII (8-10)"Group VIII"! noble metal component. Preferably the metal componentcomprises uniformly dispersed platinum and another Group VIII metal as asurface-layer component. Most preferably, the surface-layer componentcomprises palladium or ruthenium and gradients of the metals aredetermined by SEM. Optimally, the nonacidic L-zeolite is potassium-formL-zeolite.

In another aspect, the invention is a reforming process, selective fordehydrocyclization of paraffins, using a bed of catalyst particlescomprising a bound nonacidic large-pore molecular sieve and amultimetallic, multigradient Group VIII (8-10) "Group VIII"! noble metalcomponent.

These as well as other objects and embodiments will become apparent fromthe detailed description of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the palladium gradient across the radius of catalystparticles in the preparations exemplified hereinafter, contrasting thepalladium gradient of control catalyst particles of the prior art withthat of catalyst particles of the invention.

FIG. 2 shows the platinum gradient across the radium of catalystparticles for control catalyst particles of the prior art and forcatalyst particles of the invention.

FIG. 3 shows the activity and stability, as well as overall selectivityto aromatics, in a reforming operation for a catalyst of the presentinvention in comparison to a prior-art control catalyst and a referencecatalyst when processing a sulfur-containing feedstock.

FIG. 4 shows the activity and stability, as well as overall selectivityto aromatics, in a reforming operation processing a low-sulfur feedstockfor a catalyst of the present invention in comparison to a prior-artcontrol catalyst.

FIG. 5 shows selectivity to aromatics in the reforming of normal heptanefor a platinum-ruthenium catalyst in comparison to a platinum-containingreference catalyst.

FIG. 6 shows the ruthenium gradient across the radius of catalystparticles of the invention.

FIG. 7 shows the effect of sulfur on selectivity to aromatics in thereforming of normal heptane for a platinum-ruthenium catalyst incomparison to a platinum-containing reference catalyst.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Broad embodiments of the present invention are directed to a bed ofcatalyst particles and reforming process using the bed of catalystparticles containing a nonacidic molecular sieve and two or more metalsof Group VIII (8-10) of the Periodic Table See Cotton and Wilkinson,Advanced Inorganic Chemistry, John Wiley & Sons (Fifth Edition, 1988)!"Group VIII noble metal"!, at least one of the metals being present inthe catalyst as a surface-layer component and at least one other metalbeing uniformly dispersed. The present reforming catalyst has been foundto be surprisingly active and stable, in comparison to catalysts of theprior art, in reforming paraffinic feedstocks to achieve high yields ofaromatics.

The invention is characterized for a bed of catalyst particles, such aswould be contained in a reaction vessel in a process unit forhydrocarbon conversion. The "bed of catalyst particles" is defined as anaggregate of catalyst particles manufactured by substantially identicalprocedures in identical equipment from the same batches of rawmaterials. The preferred catalyst particle of the present invention isan extrudate, usually cylindrical in shape and having a diameter ofabout 0.8 to 3.2 mm (especially 1.5 to 2.2 mm) and a length to diameterratio of about 1:1 to 5:1, with 2:1 to 3:1 being especially preferred.Other particle shapes known in the art are within the scope of theinvention such as spheres, rods, pills, pellets, tablets or granules;spherical particles may be formed directly or from extrudates by rollingeh extrudate particles on a spinning disk.

An essential component of the catalyst particles is a non-acidiclarge-pore molecular sieve. Suitable molecular sieves generally have amaximum free channel diameter or "pore size" of 6 Å or larger, andpreferably have a moderately large pore size of about 7 to 8 Å. Suchmolecular sieves include those characterized as AFI, BEA, FAU or LTLstructure type by the IUPAC Commission on Zeolite Nomenclature, with theLTL structure being preferred. It is essential that the preferredL-zeolite be non-acidic, as acidity in the zeolite lowers theselectivity to aromatics of the finished catalyst. In order to be"non-acidic," the zeolite has substantially all of its cationic exchangesites occupied by nonhydrogen species. Preferably the cations occupyingthe exchangeable cation sites will comprise one or more of the alkalimetals, although other cationic species may be present. An especiallypreferred nonacidic L-zeolite is potassium-form L-zeolite.

It is necessary to composite the L-zeolite with a binder in order toprovide a convenient form for use in the catalyst particles of thepresent invention. The art teaches that any refractory inorganic oxidebinder is suitable. One or more of silica, alumina or magnesia arepreferred binder materials of the present invention. One or both ofamorphous silica and alumina are especially preferred, and excellentresults are obtained when using a synthetic white silica powderprecipitated as ultra-fine spherical particles from a water solution.The silica binder preferably is nonacidic, contains less than 0.3 mass %sulfate salts, and has a BET surface area of from about 120 to 160 m²/g.

The L-zeolite and binder may be composited to form particle shapes knownto those skilled in the art such as spheres, extrudates, rods, pills,pellets, tablets or granules. Spherical particles may be formed directlyby the oil-drop method as disclosed hereinbelow or from extrudates byrolling extrudate particles on a spinning disk. In one method of formingextrudates, potassium-form L-zeolite and amorphous silica are commingledas a uniform powder blend prior to introduction of a peptizing agent. Anaqueous solution comprising sodium hydroxide is added to form anextrudable dough. The dough preferably will have a moisture content offrom 30 to 50 mass % in order to form extrudates having acceptableintegrity to withstand direct calcination. The resulting dough isextruded through a suitably shaped and sized die to form extrudateparticles, which are dried and calcined generally by known methods.Preferably, extrudates are subjected directly to calcination without anintermediate drying step in order to encapsulate potassium ions andpreserve basicity. The calcination of the extrudates is effected in anoxygen-containing atmosphere at a temperature of from about 260° to 650°C. for a period of about 0.5 to 2 hours.

An alternative alumina form of the present catalyst support is thesphere. Alumina spheres may be continuously manufactured by the wellknown oil-drop method which comprises: forming an alumina hydrosol byany of the techniques taught in the art and preferably by reactingaluminum metal with hydrochloric acid; combining the resulting hydrosolwith a suitable gelling agent; and dropping the resultant mixture intoan oil bath maintained at elevated temperatures. The droplets of themixture remain in the oil bath until they set and form hydrogel spheres.The spheres are then continuously withdrawn from the oil bath andtypically subjected to specific aging and drying treatments in oil andan ammoniacal solution to further improve their physicalcharacteristics. The resulting aged and gelled particles are then washedand dried at a relatively low temperature of about 150° to about 205° C.and subjected to a calcination procedure at a temperature of about 450°to about 700° C. for a period of about 1 to about 20 hours. Thistreatment effects conversion of the alumina hydrogel to thecorresponding crystalline gamma-alumina. U.S. Pat. No. 2,620,314provides for additional details and is incorporated herein by referencethereto.

A reforming-catalyst support may incorporate other porous, adsorptive,high-surface-area materials. Within the scope of the present inventionare refractory supports containing one or more of: (1) refractoryinorganic oxides such as alumina, silica, titania, magnesia, zirconia,chromia, thoria, boria or mixtures thereof, (2) synthetically preparedor naturally occurring clays and silicates, which may be acid-treated;(3) crystalline zeolitic aluminosilicates, either naturally occurring orsynthetically prepared such as FAU, MEL, MFI, MOR, MTW (IUPAC Commissionon Zeolite Nomenclature), in hydrogen form or in a form which has beenexchanged with metal cations; (4) spinels such as MgAl₂ O₄, FeAl₂ O₄,ZnAl₂ O₄ ; and (5) combinations of materials from one or more of thesegroups.

An alkali metal component is a highly preferred constituent of thereforming catalyst particles. One or more of the alkali metals,including lithium, sodium, potassium, rubidium, desium and mixturesthereof, may be used, with potassium being preferred. The alkali metaloptimally will occupy essentially all of the cationic exchangeable sitesof the non-acidic L-zeolite as described hereinabove. Surface-depositedalkali metal also may be present as described in U.S. Pat. No.4,619,906, incorporated herein by reference thereto.

An essential ingredient of catalyst particles of the invention is amultimetallic, multigradient Group VIII (8-10) "Group VIII"! noble-metalcomponent. "Multigradient" designates the differing distribution of twoor more Group VIII noble metals in the catalyst particle. Preferably atleast one metal is present as a "surface-layer" component as describedhereinbelow, while one or more other metals is uniformly dispersedthroughout the catalyst particle. The characterization of the Group VIIInoble metal as a "surface-layer" component is intended to encompass aGroup VIII noble-metal gradient upon and within the catalyst support asdescribed hereinbelow.

Of the Group VIII noble metals, i.e., platinum, palladium, rhodium,ruthenium, osmium and iridium, palladium is a preferred surface-layermetal and platinum is preferred as the uniformly dispersed metal.Mixtures of Group VIII noble metals as the surface-layer and/oruniformly dispersed component as also are within the scope of thisinvention. One or more of rhodium, ruthenium and iridium areparticularly suitable alternative surface-layer metals, with rutheniumbeing especially favored. The Group VIII noble-metal component may existwithin the final catalytic composite as a compound such as an oxide,sulfide, halide, or oxyhalide, in chemical combination with one or moreof the other ingredients of the composite, or as an elemental metal.Best results are obtained when substantially all of the metals arepresent in the elemental state. Each of the metals may be present in thefinal catalyst composite in any amount which is catalytically effective,but relatively small amounts are preferred. Each of the surface-layerand the uniformly dispersed Group VIII noble-metals generally willcomprise from about 0.01 to 5 mass % of the final catalyst, andpreferably about 0.05 to 2 mass %, calculated on an elemental basis. Theratio of surface-layer to uniformly dispersed metal usually is in therange of from about 20:1 to 1:50, and optimally from about 10:1 to 1:20,on an elemental mass basis.

At least one Group VIII noble metal is concentrated in the surface layerof each catalyst particle. In defining the present invention, "layer" isa stratum of a catalyst particle of substantially uniform thickness at asubstantially uniform distance from the surface of the catalystparticle. The "surface layer" is the layer of the catalyst particleadjacent to the surface of the particle. The concentration ofsurface-layer Group VIII noble metal tapers off in progressing from thesurface to the center of the catalyst particle, and is substantiallylower in the "central core" of the particle than in its surface layer."Central core" is defined, in characterizing the present invention, as acore of a catalyst particle representing 50% of the diameter or,preferably, 50% of the volume of the particle. "Diameter" is defined asthe minimum regular dimension through the center of the catalystparticle; for example, this dimension would be the diameter of thecylinder of an extrudate. For the preferred extrudates of the presentinvention, the central core is a concentric cylindrical portionexcluding the surface layer at the side and ends of the cylindricalextrudate particles; a central core having 50% of the volume of theextrudate particle generally would have a diameter 70-75% of that of theparticle. However, other quantitative criteria for measuring thegradient of metal concentration in a catalyst particle are not excludedthereby.

A "surface-layer" metal of the present catalyst has a concentration inthe surface layer of the catalyst particle that is at least twice theconcentration in the central core of the catalyst particle. Preferably,measurement of the surface-layer concentration is effected as theaverage of the concentration closest to the surface of at least threecatalyst particles. More preferably, the surface-layer concentration ofGroup VIII noble metal is at least about three times the concentrationin the central core. Alternatively, the surface-layer concentration isthe average of measurements within a surface layer which is, forexample, 100 microns deep. In thus characterizing the invention and asexemplified hereinbelow, the surface layer may be 50 to 100 microns deepor represent 10% or 20% of the radius of the catalyst particle. "Radius"is defined as the distance from the surface to the center of thecatalyst particle, being half of the diameter of the particle. In analternative definition, about 50% or more of a surface-layer metal iscontained in the surface layer of a catalyst.

The surface-layer Group VIII noble metal may be incorporated into thecatalyst particle in any manner suitable to effect a decreasing gradientof the metal from the surface to the center of the particle. Preferably,the metal is impregnated into the bound nonacidic zeolite as a compoundwhich decomposes upon contact with the bound zeolite, releasing themetal at or near the surface of the particle. More preferably, apalladium component is impregnated as a compound, especially a salt,which decomposes at a pH of about 5 or more. For example, the preferredpalladium is impregnated as Pd(NO₃)₂ which decomposes upon contacting abound L-zeolite. Other means, which do not limit the invention, includeusing a compound of the metal which complexes with the bound zeolite orwhich does not penetrate into the interior of the particle. An exampleis a multi-dented ligand, such as carboxylic acids or metal compoundscontaining amino groups, thiol groups, phosphorus groups or other polargroups which can bond strongly to an oxide support.

Alternatively, the surface-layer Group VIII noble metal may beincorporated into the catalyst by spray impregnation. One example ofthis would be to place a spray nozzle within a rotating drum which holdsa catalyst support. A solution of the salt of the surface-layer metal isejected from the nozzle using air to form fine droplets of spray, whichcontact the support in the rotating drum for effective mixing. Thevolume ratio of solution to support is sufficient to effect the desiredconcentration of surface-layer metal in the catalyst, and preferablywould be from about 0.3 to 1.0.

The gradient of the Group VIII noble metals preferably is determined byScanning Electron Microscopy ("SEM"). SEM determinations of local metalconcentrations are effected on at least three sample particles from thebed. Samples are selected from the bed by techniques known to those ofordinary skill in the art. The SEM data show the approximate metalscontent of any one point within a catalyst particle, based on the metalsdistribution profile in relation to the quantity of support. The resultof each analysis may not be based upon a zero point; attempting tointegrate a distribution curve is not possible, and could lead tointerpretation errors as the entire curve could be shifted either up ordown. However, the data are useful for making relative comparisons ofmetal distributions.

The uniformly dispersed Group VIII noble metal representing an essentialsegment of the multigradient Group VIII noble-metal component may beincorporated in the porous carrier material in any suitable manner, suchas coprecipitation, ion-exchange or impregnation. Platinum is thepreferred uniformly dispersed metal, and optimally is incorporated intothe catalyst utilizing a soluble, decomposable compound to impregnatethe carrier material in a relatively uniform manner. For example,platinum may be added to the support by commingling the latter with anaqueous solution of chloroplatinic acid, ammonium chloroplatinate,bromoplatinic acid, platinum trichloride, platinum tetrachloridehydrate, platinum dichlorocarbonyl dichloride, tetraamine platinumchloride, dinitrodiaminoplatinum, sodium tetranitroplatinate (II), andthe like. The utilization of a chloride compound is preferred since itfacilitates the uniform distribution of the metallic componentsthroughout the carrier material. In addition, it is generally preferredto impregnate the carrier material after it has been calcined in orderto minimize the risk of loss of the valuable Group VIII noble metal.Although it is within the scope of the invention that the surface-layerand uniformly dispersed Group VIII noble metals are incorporated intothe catalyst simultaneously, any effective order of addition isacceptable and the surface-layer component can be added before or afteraddition of the uniformly dispersed metal. Optimally, the surface-layercomponent is incorporated into the catalyst prior to the addition of theuniformly dispersed metal with oxidation of the composite beforeaddition of the latter metal.

As measured by SEM, a metal is considered uniformly dispersed if themetal concentration at one stratum from determinations on three or moreparticles differs by less than about 50% from the average metalconcentration on the particles. Preferably, the difference between themetal concentration at any stratum and the average for the entireparticles is less than about 25%.

It is within the scope of the present invention that the catalyst maycontain other metal components known to modify the effect of the GroupVIII noble-metal component. Such metal modifiers may include Group IVA(14) metals, rhenium, indium, gallium, manganese, zinc, uranium,dysprosium, thallium and mixtures thereof. Catalytically effectiveamounts of such metal modifiers may be incorporated into the catalyst byany means known in the art. Generally an optional metal modifier ispresent in a concentration of from about 0.01 to 5 mass % of thefinished catalyst on an elemental basis. Preferably, the catalyst doesnot contain such metal modifiers.

The reforming catalyst may contain a halogen component. The halogencomponent may be either fluorine, chlorine, bromine or iodine ormixtures thereof with chlorine being preferred. Considering thenonacidic nature of the support, the halogen usually is incorporatedinto the catalyst only in association with the incorporation of a metalcomponent. The halogen component is generally present in a combinedstate with the inorganic-oxide support. The halogen component ispreferably well dispersed throughout the catalyst and may comprise frommore than 0.2 to about 15 wt. % calculated on an elemental basis, of thefinal catalyst.

The final reforming catalyst generally will be dried at a temperature offrom about 100° to 320° C. for about 0.5 to 24 hours, followed byoxidation at a temperature of about 300° to 550° C. (preferably aboveabout 350° C.) in an air atmosphere for 0.5 to 10 hours. Preferably theoxidized catalyst is subjected to a substantially water-free reductionstep at a temperature of bout 300° to 550° C. (preferably above about350° C.) for 0.5 to 10 hours or more. The duration of the reduction stepshould be only as long as necessary to reduce the platinum, in order toavoid pre-deactivation of the catalyst, and may be performed in-situ aspart of the plant startup if a dry atmosphere is maintained. Furtherdetails of the preparation and activation of embodiments of thesulfur-sensitive reforming catalyst are disclosed, e.g., in U.S. Pat.Nos. 4,619,906 (Lambert et al.) and 4,882,762 (Ellig et al.), which areincorporated into this specification by reference thereto.

A hydrocarbon feedstock to the present reforming process comprisesparaffins and naphthenes, and may comprise aromatics and small amountsof olefins, preferably boiling within the gasoline range. Feedstockswhich may be utilized include straight-run naphthas, natural gasoline,synthetic naphthas, thermal gasoline, catalytically cracked gasoline,partially reformed naphthas or raffinates from extraction of aromatics.The distillation range may be that of a full-range naphtha, having aninitial boiling point typically from 40°-80° C. and a final boilingpoint of from about 160°-210° C., or it may represent a narrower rangewithin a lower final boiling point. Light paraffinic feedstocks, such asnaphthas from Middle East crudes having a final boiling point of fromabout 100°-160° C., are preferred due to the specific ability of theprocess to dehydrocyclize paraffins to aromatics. Raffinates fromaromatics extraction, containing principally low-value C₆ -C₈ paraffinswhich can be converted to valuable B--T--X aromatics, are especiallypreferred feedstocks.

The hydrocarbon feedstock to the present process may contain smallamounts of sulfur compounds, amounting to generally less than 10 partsper million (ppm) on an elemental basis. Preferably the hydrocarbonfeedstock has been prepared by a conventional pretreating step such ashydrotreating, hydrorefining or hydrodesulfurization to convert suchcontaminants as sulfurous, nitrogenous and oxygenated compounds to H₂ S,NH₃ and H₂ O, respectively, which then can be separated from thehydrocarbons by fractionation. This pretreating preferably will employ acatalyst known to the art comprising an inorganic oxide support andmetals selected from Groups VIB(6) and VIII(9-10). Alternatively or inaddition to the conventional hydrotreating, the pretreating step maycomprise contact with sorbents capable of removing sulfurous and othercontaminants. These sorbents may include but are not limited to one ormore of zinc oxide, iron sponge, high-surface-area sodium,high-surface-area alumina, nickel-on-alumina, activated carbons andmolecular sieves. Preferably, the pretreating step will provide thereforming catalyst with a hydrocarbon feedstock having sulfur levels atleast as low as disclosed in the prior art as desirable reformingfeedstocks, e.g., 1 ppm to 0.1 ppm (100 ppb); sulfur levels of 0.5 to0.15 ppm are usual in modern pretreating units.

Optionally, the hydrocarbon feedstock is essentially sulfur-free.Selective reforming catalysts for aromatization of paraffins are knownto be highly sulfur-sensitive, and some benefit may be derived from asulfur-free feedstock even when utilizing the present active, stablecatalyst. Sulfur-free is defined as containing less than 20 parts perbillion (ppb), and preferably less than 14 ppb, sulfur. Therepeatability of the American National Standard test ASTM D 4045-87 is20 ppb at a sulfur level of 0.02 ppm (20 ppb), and "sulfur free"according to this test therefore would be defined as less than 20 ppbsulfur. It is believed, however, that one laboratory testing a series ofsimilar samples can detect differences at lower sulfur levels, e.g., 10μg/ml or 14 ppb sulfur.

Operating conditions used in the process of the present inventioninclude a pressure of from about atmospheric to 60 atmospheres(absolute), with the preferred range being from atmospheric to 20atmospheres and a pressure of below 10 atmospheres being especiallypreferred. Free hydrogen preferably is supplied to the process in anamount sufficient to correspond to a ratio of from about 0.1 to 10 molesof hydrogen per mole of hydrocarbon feedstock. By "free hydrogen" ismeant molecular H₂, not combined in hydrocarbons or other compounds.Preferably, the reaction is carried out in the absence of added halogen.The volume of catalyst corresponds to a liquid hourly space velocity offrom about 0.5 to 40 hr⁻¹. The operating temperature generally is in therange of 260° to 600° C. Temperature selection is influenced by productobjectives, with higher temperatures effecting higher conversion toaromatics and light hydrocarbons. Hydrocarbon types in the feedstockalso influence temperature selection, as naphthenes are largelydehydrogenated over the first portion of the reforming catalyst whichthe feedstock contacts with a concomitant sharp decline in temperatureacross the first catalyst bed due to the endothermic heat of reaction.The temperature generally is slowly increased during each period ofoperation to compensate for inevitable catalyst deactivation.

The reforming process may be effected in a reactor section comprisingone reactor or in multiple reactors with provisions known in the art toadjust inlet temperatures to individual reactors. The feed may contactthe catalyst system in each of the respective reactors in either upflow,downflow, or radial-flow mode. Since the preferred reforming processoperates at relatively low pressure, the low pressure drop in aradial-flow reactor favors the radial-flow mode. As the predominantdehydrocyclization and dehydrogenation reactions are endothermic, thereactor section generally will comprise two or more reactors withinterheating between reactors to compensate for the endothermic heat ofreaction and maintain dehydrocyclization conditions.

The reforming process will produce an aromatics-rich effluent stream,with the aromatics content of the C₅ + portion of the effluent typicallywithin the range of about 45 to 85 mass %. The composition of thearomatics will depend principally on the feedstock composition andoperating conditions, and generally will consist principally of C₆ -C₁₂aromatics. Benzene, toluene and C₈ aromatics will be the primaryaromatics produced from the preferred light naphtha and raffinatefeedstocks.

Using techniques and equipment known in the art, the aromatics-richeffluent usually is passed through a cooling zone to a separation zone.In the separation zone, typically maintained at about 0° to 65° C., ahydrogen-rich gas is separated from a liquid phase. The resultanthydrogen-rich stream can then be recycled through suitable compressingmeans back to the first reforming zone. The liquid phase from theseparation zone is normally withdrawn and processed in a fractionatingsystem in order to adjust the concentration of light hydrocarbons andproduce an aromatics-containing reformate product.

The reactor section usually is associated with catalyst-regenerationoptions known to those of ordinary skill in the art, such as: (1) asemiregenerative unit containing fixed-bed reactors maintains operatingseverity by increasing temperature, eventually shutting the unit downfor catalyst regeneration and reactivation; (2) a swing-reactor unit, inwhich individual fixed-bed reactors are serially isolated by manifoldingarrangements as the catalyst become deactivated and the catalyst in theisolated reactor is regenerated and reactivated while the other reactorsremain on-stream; (3) continuous regeneration of catalyst withdrawn froma moving-bed reactor, with reactivation and substitution of thereactivated catalyst, permitting higher operating severity bymaintaining high catalyst activity through regeneration cycles of a fewdays; or: (4) a hybrid system with semiregenerative andcontinuous-regeneration provisions in the same unit. The preferredembodiment of the present invention is fixed-bed reactors in asemiregenerative unit.

An optional embodiment of the present invention is reforming of thehydrocarbon feedstock with a physical mixture of the reforming catalystand a sulfur sorbent. The mixture is contained either in a fixed-bedreactor or in a moving-bed reactor whereby catalyst may be continuouslywithdrawn and added. The sulfur sorbent should not only be effective forremoval of small amounts of sulfur compounds from hydrocarbon streams atreforming-catalyst operating conditions, but also be compatible with thereforming catalyst in order to maintain the activity of the catalyst.The sulfur sorbent comprises a metal oxide, preferably selected fromoxides of the metals having an atomic number between 19 and 30inclusive; these metals, particularly potassium, calcium, vanadium,manganese, nickel, copper and zinc are known to be effective for sulfurremoval in various circumstances. The sorbent optimally comprises amanganese component. Manganese oxide has been found to provide reformingcatalyst protection superior to the zinc oxide of the prior at, it isbelieved, due to possible zinc contamination of associated reformingcatalyst. The manganese oxides include MnO, Mn₃ O₄, Mn₂ O₃, MnO₃, andMn₂ O₇. The preferred manganese oxide is MnO (manganous oxide). Themanganese component may be composited with a suitable binder such asclays, graphite, or inorganic oxides including one or more of alumina,silica, zirconia, magnesia, chromia or boria in order to provide asecond particle for the physical mixture of the present catalyst system.Preferably, the manganese component is unbound and consists essentiallyof manganese oxide. Even more preferably the manganese componentconsists essentially of MnO, which has demonstrated excellent resultsfor sulfur removal and has shown adequate particle strength without abinder for the second particle of the present invention.

In yet another alternative embodiment of the present invention, thephysical mixture of reforming catalyst particles and sulfur sorbent iscontained within the same catalyst particle. In this embodiment, thecatalyst particles and sorbent may be ground or milled together orseparately to form particles of suitable size, preferably less than 100microns, and the particles are supported in a suitable matrix.Preferably, the matrix is selected from the inorganic oxides describedhereinabove.

Other embodiments and variants encompassed by and within the spirit ofthe present invention as claimed will be apparent to the skilledroutineer. Examples follow which illustrate certain specificembodiments, and these particularly should not be construed to limit thescope of the invention as set forth in the claims.

EXAMPLES

Three parameters are especially useful in evaluating reforming processand catalyst performance, particularly in evaluating catalysts fordehydrocyclization of paraffins. "Activity" is a measure of thecatalyst's ability to convert reactants at a specified set of reactionconditions. "Selectivity" is an indication of the catalyst's ability toproduce a high yield of the desired product. "Stability" is a measure ofthe catalyst's ability to maintain its activity and selectivity overtime.

The examples illustrate the effect especially on reforming catalystactivity and stability in the presence of sulfur and on activity andselectivity in the absence of sulfur of utilizing a catalyst particlesprepared in the manner disclosed in the present invention.

Example I

The feedstock on which catalyst comparisons were based was a raffinatefrom a combination of catalytic reforming followed by aromaticsextraction to recover benzene, toluene and C₈ aromatics. Thecharacteristics of the feedstock were as follows:

    ______________________________________                                        Sp. gr.         0.6896                                                        ASTM D-86, °C.:                                                        IBP             70                                                            10%             77                                                            50%             86                                                            50%             108                                                           EP              138                                                           Mass %                                                                        Paraffins       90.3                                                          Olefins         0.1                                                           Naphthenes      6.8                                                           Aromatics       2.8                                                           ______________________________________                                    

The above composition was used in tests indicated below with and withoutsmall amounts of sulfur present: Feedstock S contained about 0.4 ppm, or400 ppb (parts per billion) sulfur, while Feedstock A contained lessthan 100 ppb sulfur.

Example II

Catalytic reforming tests were performed on the above raffinatefeedstock using catalysts of the invention on comparison with catalystsof the known art. A basic catalyst as known in the art, not of theinvention an containing a single Group VII (8-10) noble metal componentconsisting essentially of platinum, was used as a "Reference" catalyst,or Catalyst R. The platinum was impregnated as tetraamineplatinumchloride (TAPC) onto an extruded silica-bound L-zeolite support having adiameter of about 1.6 mm and an L/D (length-to-diameter) ratio of 2 to 3to effect a platinum content of 0.82 mass %, on an elemental basis, ofthe finished catalyst. The catalyst was finished by oxychlorination at350° C. in air, using an HCl/Cl₂ mixture, and reduction with hydrogen at350° C.

A control Catalyst C, representing a bimetallic Group VIII (8-10) noblemetal catalyst not of the invention, was prepared from the same supportas used for Catalyst R. Platinum and palladium were coimpregnated ontothe support to achieve a uniform distribution in an atomic ratio ofabout 1:1 of the two metals. A solution of Pd (NO₃)₂ andethylenediaminetetraacetic acid (EDTA) was combined with TAPC and usedto impregnate the L-zeolite/silica support. Catalyst C was finished byoxychlorination and reduction in the manner of Catalyst R. The finishedcatalyst particles had the following composition in mass %:

    ______________________________________                                                Palladium                                                                            0.436                                                                  Platinum                                                                             0.827                                                                  Chloride                                                                             0.48                                                           ______________________________________                                    

Example III

A bed of catalyst particles of the invention was prepared by successiveimpregnation of palladium and platinum to provide an atomic ratio ofabout 1:1 on the same support used for the Reference and Controlcatalysts described hereinabove. The palladium was impregnated asPd(NO₃)₂ and precipitated substantially on the surface of the support,which then was oxidized at 565° C. The oxidized support then wasimpregnated with TAPC to provide a substantially uniform distribution ofplatinum on the support. The palladium- and platinum-impregnated supportwas finished by oxychlorination and reduction in the manner of CatalystR. The finished catalyst, designated as Catalyst A, had the followingcomposition in mass %:

    ______________________________________                                                Palladium                                                                            0.404                                                                  Platinum                                                                             0.823                                                                  Chloride                                                                             0.43                                                           ______________________________________                                    

Example IV

Catalyst particles C and A were evaluated by Scanning ElectionMicroscopy (SEM). The purpose of this analysis was to identify therelative distribution of palladium and platinum across the radius of thecatalyst particles. Three particles each of C and A were evaluated inorder to provide reliable average data.

The SEM data shows the approximate metals content of any one pointwithin the catalyst pill, as indicated hereinabove, based on the metalsdistribution profile in relation to the support. The data are useful formaking relative comparisons of metal distributions.

FIG. 1 shows the relative distribution of palladium concentration acrossthe 800-micron radius of the catalyst particles from the surface to thecenter of each particle. Control Catalyst C displayed a relatively evendistribution of palladium, with no discernable trend in concentrationacross the particles. Catalyst A, in contrast, displayed anexceptionally high concentration of palladium on a relative basis in thesurface layer of the catalyst particles. The concentration of palladiumat the surface was an order of magnitude higher than the palladiumcontent in the central core representing 50% of the volume of thecatalyst. The average palladium concentration in 50- or 100-micronsurface layers or surface layers representing 10% or 20% of the radiusof the catalyst particle can be estimated to be 5-7 times or more thatof the palladium content in the central core.

FIG. 1 shows the relative distribution of platinum concentration acrossthe 800-micron radius of the catalyst particles. Both Catalysts C and Adisplayed a relatively even distribution of platinum, with most of themeasurements falling within about 10% of the mean concentration and theextreme concentration being within about 25-30% of the mean. Platinumthus would be considered to be uniformly dispersed in both Catalysts Cand A; Reference Catalyst R is prepared with the sameplatinum-impregnation step as Catalysts C and A and thus also featuresuniformly dispersed platinum.

To quantify the differences between the catalysts of the invention andof the prior art, the relative proportions of palladium in surfacelayers were calculated from the data presented in FIG. 1. The 100-micronsurface layer represents about 27-28% of the volume of the extrudedparticle, and the proportion of palladium in the 100-micron surfacelayer of Control Catalyst C thus would be about 25-30%. In contrast,Catalyst A of the invention has 55-60% of its palladium content in the100-micron surface layer. The layer representing the outer 10% of thediameter of Catalyst A, 80 microns in depth, has about 50% or more ofthe palladium, and over 75% of the palladium is in the layerrepresenting the outer 20% of the diameter of the catalyst.

Example V

Catalyst A was tested in catalytic reforming of a sulfur-containingraffinate feedstock in comparison with Control Catalyst C and a seriesof tests of Reference Catalyst R. The feedstock was as described abovein Example I except that the raffinate contained about 400 ppb (partsper billion) of sulfur.

Operating conditions were as follows:

    ______________________________________                                        Pressure, atmospheres 4.5                                                     Hydrogen/hydrocarbon, mol                                                                           3                                                       Liquid hourly space velocity, hr.sup.-1                                                             2                                                       ______________________________________                                    

Temperature was adjusted as required to achieve approximately 50 mass %conversion of C₆ +. The comparative results are plotted in FIG. 3 andmay be summarized as follows:

    ______________________________________                                        Catalyst          A        C       R                                          ______________________________________                                        Activity, °C. initial temperature                                                        451      482+    450                                        Deactivation rate, °C./day                                                               3.1      *       4.2                                        Aromatics selectivity, mass %                                                                   83.3     <<80    81.5                                       ______________________________________                                         *Stable operation was not achieved with Catalyst C.                      

Catalyst A of the invention thus demonstrated a significant improvementin stability and selectivity, with nearly the same activity, incomparison with the Reference platinum-only Catalyst R of the art whenprocessing a sulfur-containing feedstock. The strong favorable effect ofsurface-layer palladium is shown in relation to Control Catalyst C,which never achieved a stable operation, as illustrated in FIG. 3.

Example VI

Catalyst A was tested in catalytic reforming of a low-sulfur raffinatefeedstock in comparison with a series of tests of Reference Catalyst R.The feedstock was as described above in Example I without sulfuraddition.

Operating conditions were as follows:

    ______________________________________                                        Pressure, atmospheres 8                                                       Hydrogen/hydrocarbon, mol                                                                           3                                                       Liquid hourly space velocity, hr.sup.-1                                                             3                                                       ______________________________________                                    

Temperature was adjusted as required to achieve approximately 65 mass %conversion of C₆ +. The comparative results are plotted in FIG. 4 andmay be summarized as follows:

    ______________________________________                                        Catalyst             A      R                                                 ______________________________________                                        Activity, °C. initial temperature                                                           494    492                                               Deactivation rate, °C./day                                                                  2.1    1.6                                               Aromatics selectivity, mass %                                                                      78.7   76.5                                              ______________________________________                                    

Catalyst A of the invention thus demonstrated a significant improvementin selectivity, with nearly the same activity and a small loss instability, in comparison with the Reference platinum-only Catalyst R ofthe art when processing a low-sulfur feedstock. The bed of catalystparticles of the invention thus demonstrates advantages in processingnot only a sulfur-containing feedstock but also a low-sulfur feedstockas indicated in FIG. 4.

Example VII

Catalyst B was prepared from the same support as used for Catalyst R.Platinum was impregnated onto the support as Pt(NH₃)₄ Cl₂ and rutheniumas Ru(NH₃)₆ Cl₃ to achieve an atomic ratio of about 11:1 of therespective metals. Catalyst B was finished by oxidation at 150° C. for 2hours and reduction at 350° C. for 1 hour. Finished catalyst particleshad the following composition in mass %.

    ______________________________________                                               Platinum                                                                              0.869                                                                 Ruthenium                                                                             0.041                                                                 Potassium                                                                             11.5                                                           ______________________________________                                    

Example VIII

Catalyst B was tested in catalytic reforming of a normal-heptanefeedstock in comparison with Reference Catalyst R. Operating conditionswere as follows:

    ______________________________________                                        Pressure, atmospheres                                                                              8                                                        Hydrogen/hydrocarbon, mol                                                                          3.5                                                      Mass hourly space velocity, hr.sup.-1                                                              8.2                                                      ______________________________________                                    

Temperature was adjusted for a range of conversion. Comparative resultsare plotted in FIG. 5 and show a selectivity advantage of about 3 mass-%for Catalyst B.

Example IX

The sulfur sensitivity of catalysts of the invention and of the knownart were compared. Preparation of each of the catalysts was initiallyeffected in a similar manner to those described in Example II. Theplatinum was impregnated as tetraamineplatinum chloride (TAPC) onto anextruded 15% silica/85% potassium-exchanged L-zeolite support to effecta platinum content of 0.75 mass %, on an elemental basis, of thefinished catalyst. The catalyst was finished by drying, oxidation at150° C. in air and reduction with hydrogen at 350° C. A sample ofcatalyst particles so prepared was designated Catalyst R', representingthe known art.

A portion of the catalyst particles as prepared for Catalyst R' wereprocessed further to obtain a catalyst of the invention. Ruthenium wasimpregnated onto the reduced catalyst particles using a water solutionof RuCl₃ to effect a platinum-to-ruthenium atomic ratio of about 1.4:1.Catalyst particles were finished by oxidation and reduction as describedin the previous paragraph and designated as Catalyst B'. The finishedcatalyst particles had the following composition in mass %:

    ______________________________________                                        Catalyst         R'     B'                                                    ______________________________________                                        Platinum         0.75   0.75                                                  Rutheninum       0.28   --                                                    Potassium        11.2   11.5                                                  ______________________________________                                    

A portion of each of Catalysts R' and B' were sulfided in order tocompare performance with the unsulfided catalysts. Samples of particlesof each catalyst were exposed to a stream of H₂ S in nitrogen at roomtemperature to effect a catalyst sulfur level of 200 mass parts permillion (ppm). The respective samples were designated Catalyst R'_(s)and Catalyst B'_(s).

Example X

Catalyst particles B' were evaluated by Scanning Election Microscopy(SEM) to identify the relative distribution of ruthenium across theradius of the catalyst particles. Three particles, designated #1, #2 and#3, were evaluated in order to provide reliable average data asdescribed in Example VI hereinabove. The SEM data shows the approximatemetals content of any one point within the catalyst pill, as indicatedhereinabove, based on the metals distribution profile in relation to thesupport.

FIG. 6 shows the relative distribution of ruthenium concentration acrossthe 800-micron radius of each of catalyst particles #1, #2 and #3 fromthe surface to the center of each particle. Catalyst B' displayed anexceptionally high concentration of ruthenium on a relative basis in thesurface layer of the catalyst particles. The concentration of rutheniumat the surface was an order of magnitude higher than the palladiumcontent in the central core representing 50% of the volume of thecatalyst. The proportion of the ruthenium in the 50- and 100-micronsurface layers is estimated to be, respectively, about 2/3 or more andabout 3/4 or more of the total ruthenium. The average rutheniumconcentration in the 100-micron surface layers was calculated to beabout 4 to 5 times, and the concentration in the 50-micron surface layerabout 5 to 7 times, that of the ruthenium content in the central core ofthe catalyst particles.

Example XI

The relative effect of sulfur on the performance of catalysts R',R'_(s), B', and B'_(s) was compared in the catalytic reforming of anormal-heptane feedstock. The test was carried out at atmosphericpressure. Other operating conditions were as follows:

    ______________________________________                                        Hydrogen/hydrocarbon, mol                                                                          58                                                       Mass hourly space velocity, hr.sup.-1                                                              4.3                                                      ______________________________________                                    

Temperature was adjusted over a range of 375° to 450° C. to effect arange of conversions. Comparative results are plotted in FIG. 7, showingaromatics yields as a function of temperature. The relatively smalldifference between aromatics yields for Catalysts B' and B'_(s) of theinvention indicates that selectivity is not as strongly affected bysulfur as for catalysts R' and R'_(s) as known in the art. The presentinvention showed improved catalyst sulfur tolerance.

We claim:
 1. A process for the reforming of a hydrocarbon feedstock comprising contacting the feedstock at reforming conditions to obtain an aromatics-rich effluent stream with a catalyst comprising:(a) a multigradient noble-metal component comprising platinum and surface-layer ruthenium; (b) a nonacidic large-pore molecular sieve; and, (c) an inorganic-oxide binder.
 2. The process of claim 1 wherein the reforming conditions comprise an operating pressure of from about atmospheric to 10 atmospheres and a temperature of from about 260° to 600° C.
 3. The process of claim 1 wherein the noble-metal component consists essentially of platinum and ruthenium.
 4. The process of claim 1 wherein the noble-metal component comprises uniformly dispersed ruthenium and surface-layer platinum.
 5. The process of claim 1 wherein the concentration of ruthenium in the 100-micron surface layer of particles of the catalyst is at least about twice the concentration of said metal in the central core of particles of the catalyst.
 6. The process of claim 1 wherein the concentration of ruthenium in the 100-micron surface layer of particles of the catalyst is at least about three times the concentration of said metal in the central core of particles of the catalyst.
 7. The process of claim 1 wherein the concentration of ruthenium in the 50-micron surface layer of particles of the catalyst is at least about twice the concentration of said metal in the central core of particles of the catalyst.
 8. The process of claim 1 wherein the nonacidic large-pore molecular sieve comprises nonacidic L-zeolite.
 9. The process of claim 1 wherein the binder comprises one or both of silica and alumina.
 10. A process for the reforming of a hydrocarbon feedstock comprising contacting the feedstock at reforming conditions to obtain an aromatics-rich effluent stream with a catalyst comprising:(a) a uniformly dispersed platinum component and a surface-layer ruthenium component; (b) a nonacidic L-zeolite; and, (c) an inorganic-oxide binder. 